Liquid Washing or Cleaning Composition Comprising Particulate Peracid Bleach

ABSTRACT

Aqueous, liquid compositions which comprise a surfactant, a bleaching agent and magnesium sulfate, wherein the bleaching agent comprises a particulate peroxocarboxylic acid which may optionally be coated, along with uses therefor are described.

The present invention concerns aqueous liquid washing or cleaningcompositions comprising peroxocarboxylic acid particles.

Liquid washing or cleaning compositions are subject to negativeinteractions of their components that can result in reduction of theiractivity and thus to reduction of the washing ability of the compositionbecause of chemical incompatibilities of the individual components, evenon relatively brief storage, especially if they contain water, but evenif they are free of water. This reduction in activity basically affectsall the components of the washing composition that can carry outchemical reactions in the washing process to contribute to the result ofthe washing, especially bleaching agents and enzymes, althoughsurfactant or sequestrant components responsible for dissolutionprocesses or complexing steps, especially in the presence of thosechemically reactive ingredients in liquid, especially aqueous, systemsdo not have unlimited storage stability.

The phthalimidoperoxoalkanoic acids, such as 6-phthalimidoperoxyhexanoicacid (PAP), are highly efficient bleaching agents, but they areparticularly unstable in ordinary liquid washing compositionformulations. They usually decompose completely within a few days. Evenif potential reactants with the peroxocarboxylic acids, such asunsaturated compounds, aldehydes, amines, chloride, etc., are removedfrom these liquid compositions they nevertheless decompose in thepresence of the surfactants, even if those are not oxidatively attacked.The reason for that may be that the phthalimidoperoxyalkanoic acids arestable only as substances with very low water solubility but dissolve inthe presence of surfactants. In that form they are highly reactive anddecompose in the solution not only through a bimolecular reaction withloss of singlet oxygen but also by hydrolysis to the phthalimidoalkanoicacid and H₂O₂. The latter, however, is practically inactive as a bleach,especially at low washing temperatures and in the concentrations thatoccur, so that, in sum, the bleaching action of the composition is loston storage.

It has occasionally been suggested that the problem of inadequatestability of peroxocarboxylic acids in aqueous liquid washingcompositions be solved by making up a high electrolyte concentration(for instance, up to 30% sodium sulfate in the liquid washingcomposition) to reduce the solubility of both the peroxocarboxylic acidand the surfactant as much as possible. That results in a system that ismicroscopically biphasic, with a typically liquid-crystallinesurfactant-rich phase dispersed in a continuous aqueous phase that isalmost free of surfactant. That measure can greatly reduce thedissolution of solid peroxocarboxylic acids, thus reducing the rate ofdecomposition.

However, such formulations with sodium sulfate, for example, have theproblems of phase stability and storage stability, especially undervarying climatic conditions. The solubility of sodium sulfate changesvery greatly with climatic variation. That can result in precipitationand in the growth of sulfate crystals, some of them very large, in theliquid composition. Also, the flow behavior of these compositions isunsatisfactory and production is complicated in practice, because largecrystals can form even during the production process due to formation ofsodium sulfate hydrate, and they do not redissolve in the thickenedformulation.

Another attempt to stabilize the bleaching agent consists of coating it.It is found, though, that just application of coating materials does notby any means always result in increasing the stability of PAP inparticular. Coating often actually results in destabilization of thePAP, even with the materials such as paraffin that are chemically inertin the systems under consideration here. A coating that is intended tobe soluble in use of the composition is generally a product thatcontains water and does not completely prevent diffusion of water. Thussuch a coating may indeed suppress the dissolution of the PAP but notits hydrolysis to H₂O₂.

It has often also been suggested at times that the problem can be solvedby not incorporating all the ingredients desirable for a good washing orcleaning result into the liquid medium at the same time. Instead, theuser should be provided multiple components that are combined only justbefore or during the washing or cleaning process, and which contain onlyingredients that are compatible with each other, which are used togetheronly under the application conditions. But the user often considers thejoint addition of multiple components too much trouble.

Thus there still remains the problem of preparing a storage-stableliquid composition that also contains all the components needed for goodwashing or cleaning, even if they are incompatible with each other.

The object of the present invention, that is intended to provide acontribution in this respect, is an aqueous liquid washing or cleaningcomposition containing surfactant and bleaching agent, comprising aparticulate peroxocarboxylic acid, which is characterized in that itcomprises magnesium sulfate.

The compositions according to the invention can contain magnesiumsulfate in proportions of up to 30% by weight if desired. Proportions inthe range from greater than 4% by weight to 20% by weight are preferred,and those in the range of 6% by weight to 10% by weight are particularlypreferred. Magnesium sulfate can optionally also be used in mixtureswith sodium sulfate and/or potassium sulfate.

The pH of compositions according to the invention is preferably between2 and 6, especially between 3 and 5.5 and particularly preferablybetween 3.5 and 5. The composition according to the invention cancontain water if desired in proportions up to 90% by weight, especially20% by weight to 75% by weight. However, the proportion can be higher orlower than those ranges if desired.

The proportion of peroxocarboxylic acid in the compositions according tothe invention is preferably 1% by weight to 25% by weight, especially 2%by weight to 20% by weight, and especially preferably 3% by weight to15% by weight. If the peroxocarboxylic acid is not solid at roomtemperature, it can be formulated into particulate form using inertcarrier materials in known ways. Preferably, though, a peroxocarboxylicacid that is solid at room temperature is used in an optionally coatedform. The peroxocarboxylic acids, which can also be designated asorganic peracids, can carry aliphatic and/or cyclic, includingheterocyclic and/or aromatic groups. Those that can be consideredinclude peroxoformic acid, peroxoacetic acid, peroxopropanoic acid,peroxohexanoic acid, peroxobenzoic acid and substituted derivatives ofthem such as m-chloro-peroxobenzoic acid, the mono- or di-peroxophthalicacids, 1,12-diperoxo-dodecanoic acid, nonylamidoperoxoadipic acid,6-hydroxyperoxohexanoic acid, 4-phthalimidoperoxobutanoic acid,5-phthalimidoperoxopentanoic acid, 6-phthalimidoperoxohexanoic acid,7-phthalimidoperoxohexanoic acid,N,N′-terephthaloyl-di-6-aminoperoxohexanoic acid and mixtures of them.The preferred peracids include the phthalimidoperoxyalkanoic acids,especially 6-phthalimidoperoxyhexanoic acid (PAP).

The peroxocarboxylic acid particles in the composition according to theinvention can if desired be coated. There it is important that thecoating material have as little solubility as possible in the liquidcomposition surrounding the coated peroxocarboxylic acid particles, butthat it release the coated peroxocarboxylic acid under the useconditions of the composition (high temperature, pH changes due todilution with water, or the like). A preferred coating material is onecomprising at least partially saturated fatty acids. Here the chainlength of the fatty acid is preferably greater than C₁₂. Stearic acid isparticularly preferred. It was found that the stability of PAP inparticular is very good, especially at low pH, so that a coating tostabilize PAP may be superfluous. It was found, though, that coating theperoxocarboxylic acid stabilizes the enzymes if they are included in acomposition according to the invention. Thus a PAP coating isadvantageous, especially in the presence of enzymes.

If a coating material is present, it is preferably applied to theparticulate peroxocarboxylic acid in proportions such that the coatedperoxocarboxylic acid particles comprise 5% by weight to 50% by weightcoating material. The diameters of the coated peroxocarboxylic acidparticles are preferably in the range of 100 μm to 1000 μm. Thereforeone starts with appropriately finely divided peroxocarboxylic acidmaterial and coats it with the coating material. It is preferable toproceed so that a fluidized bed of the peroxocarboxylic acid particlesbeing coated is sprayed with a solution or suspension, preferably anaqueous solution, or with a melt of the coating material. Then thesolvent or suspending agent, preferably water, if present, is removed byevaporation, or the melted coating material is solidified by cooling,and the coated peroxocarboxylic acid particles are removed from thefluidized bed in essentially the usual manner. For the coating withfatty acids as discussed, a melt coating is preferred.

Along with water, surfactant, magnesium sulfate and the optionallycoated peroxocarboxylic acid particles, a liquid washing or cleaningcomposition according to the invention can contain all the ingredientsusual in such compositions, such as, for example, solvents, builders,enzymes, and other additives such as soil repellants, thickeners,colorants and fragrances or the like.

A preferred embodiment contains nonionic surfactants and/or organicsolvents as well as optionally anionic surfactants, cationicsurfactants, and/or amphoteric surfactants.

Surfactants of the sulfonate type, alk(en)yl sulfates, alkoxylatedalk(en)yl sulfates, ester sulfonates and/or soaps are preferred asanionic surfactants.

The surfactants of the sulfonate type that are considered preferable areC₉-C₁₃-alkylbenzenesulfonates, olefin sulfonates, i.e., mixtures ofalkene and hydroxyalkane sulfonates, and disulfonates, such as areobtained, for instance, from C₁₂-C₁₈ monoolefins with terminal orinternal double bonds, by sulfonation with gaseous sulfur trioxide andsubsequent alkaline or acidic hydrolysis of the sulfonation products.

The preferred alk(en)yl sulfates are the alkali salts, preferably thesodium salts, of the sulfuric acid hemiesters of the C₁₀-C₁₈-fattyalcohols such as those of coco fatty alcohol, tallow fatty alcohol,lauryl, myristyl, cetyl or stearyl alcohol, or the C₈-C₂₀-oxoalcoholsand those hemiesters of secondary alcohols having that chain length.Also preferred are alk(en)yl sulfates of the specified chain length thatcontain a synthetic straight-chain alkyl group made on a petrochemicalbasis. The C₁₂-C₁₆-alkyl sulfates, C₁₂-C₁₅-alkyl sulfates, C₁₄-C₁₅-alkylsulfates and C₁₄-C₁₆-alkyl sulfates are particularly preferred from theviewpoint of laundry technology. 2,3-alkyl sulfates, such as can beobtained as commercial products of the Shell Oil Company under the DAN®name, are also suitable anionic surfactants.

The sulfuric acid hemiesters of straight-chain or branched-chainC₇-C₂₁-alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as2-methyl branched C₉-C₁₁-alcohols having an average of 3.5 moles ofethylene oxide (EO) or C₁₂-C₁₈-fatty alcohols having 1 to 4 EO aresuitable. They are usually used only in relatively low proportions inlaundry compositions because of their high foaming, for instance, inproportions of 0 to 5% by weight.

The esters of α-sulfofatty acids (ester sulfonates), such as theα-sulfonated methyl esters of hydrogenated coco, palm nut or tallowfatty acids are also suitable.

Soaps in particular can be considered as other anionic surfactants.Saturated fatty acid soaps are particularly suitable, such as the saltsof lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenatederucic acid and behenic acid, and particularly those derived fromnatural fatty acids, such as coco, palm nut or tallow fatty acids.Particularly preferred soap mixtures are those made up of 50 to 100% byweight saturated C₁₂-C₂₄ fatty acids and 0 to 50% by weight of oleicacid soap.

A further class of anionic surfactants is the class of ether carboxylicacids accessible by reaction of fatty alcohol ethoxylates with sodiumchloroacetate in the presence of basic catalysts. They have the generalformula:

RO—(CH₂—CH₂—O)_(p)—CH₂—COOH

with R=C₁-C₁₈ and p=0.1 to 20. Ether carboxylic acids are not sensitiveto water hardness and exhibit outstanding surfactant properties.

Cationic surfactants contain the high-molecular-weight hydrophobic groupthat causes the surface activity in the cation when they dissociate inaqueous solution. The major representatives of the cationic surfactantsare the quaternary ammonium compounds having the general formula:(R¹R²R³R⁴N⁺)X⁻. Here R¹ stands for C₁-C₈-alk(en)yl, R² to R⁴,independently of each other, stand forC_(n)H_(2n+1−p−x)—(Y¹(CO)R⁵)_(p)—(Y₂H)_(x), in which n stands forintegers other than zero, and p and x stand for integers or zero. Y¹ andY², independently of each other, stand for O, N or NH. R⁵ designates aC₃-C₂₃-alk(en)yl chain. X is a counterion, preferably selected from thegroup of alkyl sulfates and alkyl carbonates. Cationic surfactants inwhich the nitrogen group is substituted with two long acyl groups andtwo short alk(en)yl groups are especially preferred.

Amphoteric or ampholytic surfactants have multiple functional groupsthat can ionize in aqueous solution and, depending on the conditions ofthe medium, give the compounds anionic or cationic character. Near theisoelectric point the anionic surfactants form internal salts, so thatthey can be poorly soluble or insoluble in water. Amphoteric surfactantsare subdivided into ampholytes and betaines, with the latter occurringas zwitterions in solution. Ampholytes are amphoteric electrolytes,i.e., compounds having both acidic and basic hydrophilic groups, whichtherefore act acidic or basic, depending on the conditions. Compoundshaving the atomic grouping R₃N⁺—CH₂—COO⁻ which exhibit the typicalproperties of zwitterions are called betaines.

The nonionic surfactants used preferably are alkoxylated and/orpropoxylated, especially primary, alcohols having preferably 8 to 18 Catoms and an average of 1 to 12 moles of ethylene oxide (EO) and/or 1 to10 moles of propylene oxide (PO) per mole of alcohol. C₈-C₁₆-alcoholalkoxylates are specially preferred, as are advantageously ethoxylatedand/or propoxylated C₁₀-C₁₅-alcohol alkoxylates, especiallyC₁₂-C₁₄-alcohol alkoxylates having a degree of ethoxylation between 2and 10, preferably between 3 and 8, and/or a degree of propoxylationbetween 1 and 6, preferably between 1.5 and 5. The stated degrees ofethoxylation and propoxylation are statistical averages, which can beintegers or fractional numbers for a particular product. Preferredalcohol ethoxylates and propoxylates have a narrow homolog distribution(narrow range ethoxylates/propoxylates, NRE/NRP). In addition to thosenonionic surfactants, it is also possible to use fatty alcohols withmore than 12 EO. Examples of those are (tallow) fatty alcohols having 14EO, 16 EO, 20 EO, 30 EO or 40 EO.

Alkyl glycosides having the general formula RO(G)_(x) can also be usedas other nonionic surfactants, e.g., as compounds, preferably withanionic surfactants, in which R indicates a primary straight-chain ormethyl-branched aliphatic group, especially methyl-branched at the 2position, having 8 to 22, preferably 12 to 18 C atoms, and G is thesymbol for a glycose unit having 5 or 6 carbon atoms, preferably forglucose. The degree of oligomerization, x, which indicates thedistribution of monoglycosides and oligoglycosides, is an arbitrarynumber between 1 and 10. Preferably, x is 1.1 to 1.4.

Another class of nonionic surfactants used preferably, either as theonly nonionic surfactants or in combination with other nonionicsurfactants, especially together with alkoxylated fatty alcohols and/oralkyl glycosides, is that of the alkoxylated, preferably ethoxylated orethoxylated and propoxylated fatty acid alkyl esters, preferably having1 to 4 carbon atoms in the alkyl chain, especially fatty acid methylesters. The C₁₂-C₁₈-fatty acid methyl esters having an average of 3 to15 EO, especially having an average of 5 to 12 EO, are particularlypreferred.

Nonionic surfactants of the amine oxide type, such asN-cocoalkyl-N,N-dimethylamine oxide andN-tallow-alkyl-N,N-dihydroxyethylamine oxide, and the fatty acidalkanolamides, can also be suitable. The proportion of these nonionicsurfactants is preferably not more than that of the ethoxylated fattyalcohols, particularly not more than half of that.

The so-called gemini surfactants can also be considered as surfactants.By this we mean generally those compounds that contain two hydrophilicgroups and two hydrophobic groups per molecule. These groups are, as arule, separated by a so-called “spacer”. This spacer is generally acarbon chain that should be long enough that the hydrophilic groups areseparated sufficiently that they can act independently of each other.Such surfactants are generally distinguished by unusually low criticalmicelle concentrations and the ability to reduce greatly the surfacetension of water. In special cases, though, the term ‘geminisurfactants’ is understood to mean not just dimeric but also trimericsurfactants.

Examples of suitable gemini surfactants include sulfated hydroxy-mixedethers or dimer alcohol-bis and trimer alcohol-tris-sulfates and -ethersulfates. End-group capped dimeric and trimeric mixed ethers areparticularly distinguished by their bifunctionality andmultifunctionality. The end-group-capped surfactants have good wettingproperties and are low-foaming, so that they are particularly suitablefor use as machine washing or cleaning compositions.

Gemini-polyhydroxyfatty acid amides or poly-polyhydroxyfatty acid amidescan also be used.

The proportion of surfactants in the compositions according to theinvention is preferably 0.1% by weight to 50% by weight, especially 10%by weight to 40% by weight, and especially preferably 20% by weight to70% by weight. It is preferable to use only mixtures of anionic andnonionic surfactants.

Polydiols, ethers, alcohols, ketones, amides and/or esters can be usedpreferably as organic solvents, in proportions of 0 to 90% by weight,preferably 0.1 to 70% by weight, particularly 0.1 to 60% by weight,based on the proportion of water present. Low-molecular-weight polarsubstances are preferred, such as methanol, ethanol, propylenecarbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate,2-propanol, ethylene glycol, propylene glycol, glycerol, diethyleneglycol, dipropylene glycol monomoethyl ether and dimethylformamide ormixtures of them.

Enzymes to be considered are in particular those of the class ofhydrolases, such as the proteases, esterases, lipases or lipolyticallyacting enzymes, amylases, cellulases or other glycosylhydrolases, andmixture of the enzymes named. In the laundry, all these hydrolasescontribute to removal of spots, such as spots containing protein, fat orstarch, and graying. Cellulases and other glycosylhydrolases cancontribute to color retention and to increasing the softness of thetextile by removal of pilling and microfibrils. Oxidoreductases can alsobe used for bleaching or to limit color transfer.

Enzymatic agents obtained from bacterial strains or fungi, such asBacillus subtilis, Bacillus licheniformis, Streptomyces griseus andHumicola insolens are particularly well suited. It is preferable to useproteases of the subtilisin type and especially proteases obtained fromBacillus lentus. Enzyme mixtures are of special interest, such asmixtures of protease and amylase, or protease and lipase orlipolytically acting enzymes, or protease and cellulase, or cellulaseand lipase or lipolytically acting enzymes, or mixtures of protease,amylase and lipase or lipolytically acting enzymes, or protease, lipaseor lipolytically acting enzymes and cellulase, but especially mixturescontaining protease and/or lipase or mixtures with lipolytically actingenzymes. Examples of such lipolytically acting enzymes are thewell-known cutinases. Peroxidases or oxidases have also proved suitablein some cases. The suitable amylases include in particular α-amylases,iso-amylases, pullulanases and pectinases. The cellulases usedpreferably are cellobiohydrolases, endoglucanases and β-glucosidases,also called cellobiases, or mixtures of them. As the various cellulasetypes differ in their CMCase and Avicelase activities, the desiredactivities can be adjusted by deliberate mixtures of the cellulases.

The proportion of enzymes or enzyme mixtures can, for example, be about0.1 to 5% by weight, preferably 0.1 to about 3% by weight. It ispreferable to formulate them in particulate form in the compositionsaccording to the invention.

Further components of laundry detergents can be builders, co-builders,soil repellants, alkaline salts, foam inhibitors, complexing agents,enzyme stabilizers, antiredeposition agents, optical brighteners and UVabsorbers.

For example, finely crystalline synthetic zeolite containing bound watercan be used as the builder, preferably Zeolite A and/or P. Zeolite MAP®(commercial product of Crosfield), for instance, is particularlypreferred as Zeolite P. However, Zeolite X is also suitable, as aremixtures of A, X and/or P. A co-crystallized sodium potassium aluminumsilicate of Zeolite A and Zeolite X, available as VEGOBOND AX®(commercial product of Condea) is also of special interest. The zeolitecan preferably be used as the spray-dried powder. If the zeolite is usedas the suspension, it can contain minor additions of nonionicsurfactants as stabilizers, such as 1 to 3% by weight, based on thezeolite, of ethoxylated C₁₂-C₁₈ fatty alcohols having 2 to 5 ethyleneoxide groups, C₁₂—CO₁₄ fatty alcohols having 4 to 5 ethylene oxidegroups, or ethoxylated isotridecanols. Suitable zeolites have an averageparticle size of less than 10 μm (volume distribution; measuring method:Coulter counter) and contain preferably 18 to 22% by weight, especially20 to 22% by weight, bound water. Phosphates can also be used as buildersubstances.

Crystalline lamellar sodium silicates having the general formulaNaMSi_(x)O_(2x+1).y H₂O, in which M means sodium or hydrogen, x is anumber from 1.9 to 4 and y is a number from 0 to 20, and preferredvalues for x are 2, 3 or 4, are suitable substitutes or partialsubstitutes for zeolites and phosphates. Preferred crystalline lamellarsilicates having the formula stated are those in which M stands forsodium and x has the value of 2 or 3. In particular, both β- andδ-sodium disilicate, Na₂Si₂O₅.y H₂O.

The preferred builder substances also include amorphous sodium silicateswith the Na₂O:SiO₂ ratio of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 andparticularly 1:2 to 1:2.6, with delayed dissolution and secondarywashing properties. The delayed dissolution, in comparison with theordinary commercial amorphous sodium silicates, can be produced invarious ways, such as by surface treatment, compounding,compacting/compression or by overdrying. In the context of thisinvention the term “amorphous” is also understood to mean “X-rayamorphous”. This means that the silicates do not produce sharp X-rayreflections in X-ray diffraction experiments, such as are typical ofcrystalline substances, but always show one or more maxima of thescattered X-radiation with a width of several degrees of diffractionangle. However, there can be very good to particularly good builderproperties if the silicate particles give diffuse or even sharpdiffraction maxima in electron diffraction experiments. This can beinterpreted that the products have microcrystalline regions of sizes of10 to a few hundreds of nm, with values up to a maximum of 50 nm, andespecially up to a maximum of 20 nm, preferred. Compressed/compactedamorphous silicates, compounded amorphous silicates, and overdriedX-ray-amorphous silicates are particularly preferred.

It is obviously also possible to use the generally known phosphates asbuilder substances, as long as such use need not be avoided forecological reasons. The sodium salts of the orthophosphates, thepyrophosphates, and particularly the tripolyphosphates are especiallysuitable. Their proportion is generally not greater than 25% by weight,preferably not greater than 20% by weight, based on the finishedcomposition in each case. It has been found in some cases thattripolyphosphates in particular, even at low proportions up to a maximumof 10% by weight, based on the finished composition, combined with otherbuilder substances, lead to a synergistic improvement of the secondarywashing ability. Preferred proportions of phosphates are less than 10%by weight, especially 0% by weight.

Organic builders usable as co-builders are, for example, thepolycarboxylic acids that are usable as their sodium salts. The term‘polycarboxylic acids’ is understood to mean those carboxylic acidshaving more than one acid function. Examples of them are citric acid,adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid,maleic acid, fumaric acid, sugar acids, aminocarboxylic acids,nitrilotriacetic acid (NTA) and their derivatives or mixtures of them.Preferred salts are the salts of the polycarboxylic acids such as citricacid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugaracids and mixtures of those.

The acids themselves can also be used. Beside their builder action, theacids typically have the property of an acidification component, and soalso serve to establish a lower and gentler pH for washing or cleaningcompositions. Of those, citric acid, succinic acid, glutaric acid,adipic acid, gluconic acid, and arbitrary mixtures of them must bementioned. Other usable acidification agents are the known pH regulatorssuch as sodium bicarbonate and sodium bisulfate.

Polymeric polycarboxylates are also suitable as builders. Examplesinclude the alkali metal salts of polyacrylic acid or polymethacrylicacids, such as those having a relative molecular weight of 500 to 70,000g/mol.

In the sense of this document, the molecular weights stated forpolymeric polycarboxylates are weight-average molecular weights, M_(w)of the particular acid form, basically determined by gel permeationchromatography (GPC) using a UV detector. The measurement is made withrespect to an external polyacrylic acid standard, which gives realisticmolecular weight values because of its structural relation with thepolymers being examined. These values differ clearly from the molecularweight figures found when polystyrene sulfonic acids are used asstandards. The molecular weights measured versus polystyrene sulfonicacids are as a rule distinctly higher than the molecular weights statedin this document.

Suitable polymers are, in particular, polyacrylates, preferably havingmolecular weights of 2,000 to 20,000 g/mol. The short-chainpolyacrylates having molecular weights of 2,000 to 10,000 g/mol, again,are preferred because of their superior solubility, with molecularweights of 3,000 to 5,000 g/mol particularly preferred.

Suitable polymers can also comprise substances consisting wholly orpartially of units of vinyl alcohol or its derivatives.

Copolymeric polycarboxylates are also suitable, especially those ofacrylic acid with methacrylic acid and of acrylic acid or methacrylicacid with maleic acid. Copolymers of acrylic acid with maleic acid thatcontain 50 to 90% by weight acrylic acid and 50 to 10% by weight maleicacid have proved to be particularly suitable. Their relative molecularweights, based on the free acids, are generally 2,000 to 70,000 g/mol,preferably 20,000 to 50,000 g/mol, and particularly 30,000 to 40,000g/mol. The (co)polymeric polycarboxylates can be used either as theaqueous solution or, preferably, as the powder.

The polymers can also contain allylsulfonic acids, such asallyloxybenzenesulfonic acid and methallylsulfonic acid as monomers toimprove the water solubility.

Biodegradable polymers of more than two different monomer units areespecially preferred, such as those containing as the monomers salts ofacrylic acid and maleic acid as well as vinyl alcohol or vinyl alcoholderivatives, or containing as monomers salts of acrylic acid and of2-alkylallylsulfonic acid and sugar derivatives.

Other preferred copolymers are those having as monomers preferablyacrolein and acrylic acid/acrylic acid salts or acrolein and vinylacetate.

Other suitable builder substances are polyacetals, which can be obtainedby reacting dialdehydes with polycarboxylic acids having 5 to 7 C atomsand at least 3 hydroxyl groups. Preferred polyacetals are obtained fromdialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde andmixtures of them, and from polyol carboxylic acids such as gluconic acidand/or glucoheptonic acid.

Other suitable organic builder substances are dextrins, such asoligomers or polymers of carbohydrates, which can be obtained by partialhydrolysis of starches. The hydrolysis can be done by usual processes,such as acid-catalyzed or enzyme-catalyzed processes. They arepreferably hydrolysis products with average molecular weights in therange of 400 to 500,000 g/mol, such as oligomers of polymers ofcarbohydrates, which can be obtained by partial hydrolysis of starches.The hydrolysis can be done by usual processes, such as acid-catalyzed orenzyme-catalyzed processes. They are preferably hydrolysis products withaverage molecular weights in the range of 400 to 500,000 g/mol. Apolysaccharide with a dextrose equivalent (DE) in the range of 0.5 to40, especially 3 to 30, is preferred, where DE is a useful measure ofthe reducing action of a polysaccharide in comparison with dextrose,which has a DE of 100. Maltodextrins with a DE between 3 and 20 and dryglucose syrups with a DE between 20 and 37 are usable, as are also theso-called yellow dextrins and white dextrins with higher molecularweights in the range of 2,000 to 30,000 g/mol.

The oxidized derivatives of such dextrins are products of their reactionwith oxidizing agents which are able to oxidize at least one alcoholfunction of the saccharide ring to the carboxylic acid function. Theseare products oxidized at C₆ and/or, in the case of ring opening of thesaccharide ring at C₂/C₃. A product oxidized at C₆ of the saccharidering can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferablyethylenediamine disuccinate, are other suitable cobuilders. It ispreferable to use ethylendiamine-N,N′-disuccinate (EDDS) in the form ofits sodium or magnesium salt. Glycerol disuccinate and glyceroltrisuccinate are also preferred in this connection. Suitable proportionsare 3 to 15% by weight in formulations containing zeolite and/orsilicate.

Other usable organic cobuilders are, for example, acetylatedhydroxycarboxylic acids or their salts, which can optionally also be inthe lactone form and which contain at least 4 carbon atoms and at leastone hydroxyl group, as well as no more than two acid groups.

The compositions can also contain components which positively influencethe ability to wash oil and grease out of textiles. These are calledsoil repellants. This effect becomes particularly apparent if a textilepreviously washed several times with a laundry detergent according tothe invention that contains these oil-dissolving and grease-dissolvingcomponents is made dirty. The preferred oil-dissolving andgrease-dissolving components include, for example, nonionic celluloseethers such as methylcellulose and methylhydroxypropylcellulose having15 to 30% by weight methoxyl groups and 1 to 15% by weight hydroxypropylgroups, based in each case on the nonionic cellulose ether, as well aspolymers of phthalic acid and/or terephthalic acid or their derivatives,known at the state of the art, especially polymers of ethyleneterephthalates and/or or polyethylene glycol tetephthalates oranionically and/or nonionically modified derivatives of them. Of these,the sulfonated derivatives of phthalic acid and terephthalic acidpolymers are particularly preferred.

It can be advantageous to add the usual foam inhibitors to compositionsfor use in washing machines. Examples of suitable foam inhibitors aresoaps of natural or synthetic origin having a high proportion of C₁₈-C₂₄fatty acids. Suitable non-surfactant-like foam inhibitors include, forexample, organopolysiloxanes and mixtures of them with microfine,optionally silanized silicic acid, as well as paraffins, waxes,microcrystalline waxes and mixtures of them with silanized silicic acidor bistearylethylenediamide. Mixtures of various foam inhibitors, suchas mixtures of silicones, paraffins or waxes are also used to advantage.

The salts of polyphosphonic acids can be considered as complexing agentsor as stabilizers, especially for enzymes that are sensitive to heavymetal ions. The sodium salts of, for example,1-hydroxyethan-1,1-diphosphonate are used preferably, as well as thoseof diethylenetriaminepentamethylene phosphonate orethylenediaminetetramethylene phosphonate, in proportions of 0.1% byweight to 5% by weight in the composition. Nitrogen-free complexingagents are preferred.

Antiredeposition agents have the function of keeping dirt removed fromthe fibers suspended in the liquor and thus preventing reattachment ofthe dirt. Colloids, mostly of organic nature, are suitable for this,such as the water-soluble salts of (co)polymeric carboxylic acids, glue,gelatins, salts of ether carboxylic acids or ether sulfonic acids ofstarch or of cellulose, or salts of acidic sulfuric acid esters ofcellulose or of starch. Polyamides containing water-soluble acidicgroups are also suitable for this purpose. Soluble starch preparationsand starch products other than those named above can also be used, suchas degraded starches, aldehyde starches, etc. Polyvinylpyrrolidone isalso usable. However, it is preferable to use cellulose ethers such ascarboxymethylcellulose (sodium salt), methylcellulose,hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methyl hydroxypropylcellulose, methylcarboxymethylcellulose, and mixtures of them, as well aspolyvinylpyrrolidone at, for instance, proportions of 0.1 to 5% byweight, based on the composition.

The compositions can contain optical brighteners, such as derivatives ofdiaminostilbenesulfonic acid or their alkali metal salts. For example,salts of4,4′-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2′-disulfonicacid or compounds of similar structure having in place of the morpholinogroup a diethanolamino group, a methylamino group, an anilino group, ora 2-methoxyethylamino group. Brighteners of the substituteddiphenylstyryl type can also be present, such as the alkali salts of4,4′-bis(2-sulfostyryl)-diphenyl,4,4′-bis(4-chloro-3-sulfostyryl)diphenyl, or4-(4-chlorostyryl)-4′-(2-sulfostyryl)diphenyl). Mixtures of thebrighteners named above can also be used.

UV absorbers can also be used. Those are compounds with marked abilityto absorb ultraviolet radiation. They are light-protection agents (UVstabilizers) and contribute to improving the light resistance of dyes,pigments and textile fibers. They also protect the skin of the wearer oftextile products from UV radiation penetrating through the textile. Ingeneral, these compounds that act by nonradiative deactivation arederivatives of benzophenone, with substituents such as hydroxy and/oralkoxy groups, mostly in the 2- and/or 4-positions. Substitutedbenzotriazoles are also suitable, as well as acrylates substituted withphenyl in the 3 position (cinnamic acid derivatives), optionally withcyano groups in the 2 position; salicylates; organic nickel complexes;and natural materials such as umbelliferone and the body's own urocanicacid. In a preferred embodiment, the UV absorbers absorb UV-A and UV-Bradiation and optionally UV-C radiation, radiating back the wavelengthsof blue light, so that they also have the effect of optical brighteners.Other preferred UV absorbers are triazine derivatives such ashydroxyaryl-1,3,5-triazines, sulfonated 1,3,5-triazine,o-hydroxyphenylbenzotriazole and 2-aryl-2H-benzotriazoles as well asbis(anilinotriazinylamino)stilbenedisulfonic acid and its derivatives.Pigments that absorb ultraviolet radiation, such as titanium dioxide,can also be used as UV absorbers.

The compositions can optionally also comprise other commonly usedthickeners and antisettling agents as well as viscosity regulators suchas polyacrylates, polycarboxylic acids, polysaccharides and theirderivatives, polyurethanes, polyvinylpyrrolidones, castor oilderivatives, polyamine derivatives such as quaternized and/orethoxylated hexamethylenediamine and arbitrary mixtures of them.Preferred compositions have a viscosity between 100 and 100,000 mPa·swhen measured with a Brookfield viscosimeter at a temperature of 20° C.and a shear rate of 20 min⁻¹. The compositions can comprise othertypical components of washing or cleaning compositions such as perfumesand/or colorants. The preferred colorants are those that have no, ornegligible, staining action on the textiles being washed. Preferredproportions for the totality of colorants used are less than 1% byweight, and preferably less than 0.1% by weight, based on thecomposition. The composition can optionally comprise white pigments suchas TiO₂.

Preferred compositions have densities of 0.5 to 2 g/cm³, especially 0.7to 1.5 g/cm³. The density difference between the peroxocarboxylic acidparticles and the liquid phase of the composition is preferably notgreater than 10% of the density of one of the two, and is particularlyso low that the peroxocarboxylic acid particles and preferably othersolid particles that may occur in the composition float in the liquidphase.

EXAMPLES Example 1 Preparation of a Composition According to theInvention

A composition E1 with the following composition (in percent by weight)was prepared in a glass vessel with a propeller stirrer:

16.5% LAS (Maranil®, Cognis) 10% Dehydrol® LT 7 (Cognis) 1% Sequion® 10H60 (Polygon Chemie) 0.3% Xanthan gum (Kelco)

8% Magnesium sulfate3% Cinnamic acid4% PAP Granulation (Eureco® W, Solvay), having a 20% by weight coating(based on the granulation) of stearic acid, made by melt-coating in afluidized bed apparatus (Aeromatic)

3% Protease Granulation (Everlase®, Novozymes) 0.2% Silicone oil (WackerChemie) 1% Fragrance

NaOH to adjust the pH to 5.0Water to make 100%.

Water was put into the stirred vessel and mixed with the xanthan gum.Then magnesium sulfate and citric acid were dissolved. Then thesurfactant and phosphonate were added. After degassing, the solids,coated PAP and the enzyme granulation were added, and then the remainingcomponents.

Example 2 Comparison Example 1

A composition V1 was made up as in Example 1, except that it containedno magnesium sulfate (replaced with water).

Example 3 Comparison Example 2

A composition V2 was made up as in Example 1, except that magnesiumsulfate was replaced with the same amount of sodium sulfate.

Example 4 Characterization

The compositions from Examples 1 to 3 were evaluated for phase stabilityand loss of the bleaching agent. The characterization was done afterstorage for 1 week under alternating climate conditions (temperaturecycles between 25° C. and 40° C.) and a constant 35° C.

The following results were obtained:

Storage in alternating climate: Crystal formation: E1: no; V1: no; V2:yes Phase stability: E1: OK; V1: OK; V2: phase separation Storage at 35°C.: Crystal formation: E1: no; V1: no; V2: no Phase stability: E1: OK;V1: OK; V2: OK PAP loss: E1: 8%; V1: 25%; V2: not determinedV1 showed an unacceptable loss of bleaching agent. V2 showed crystalformation and phase instability under alternating climate conditions.The advantages of E1 are predominant.

1-10. (canceled)
 11. An aqueous, liquid composition comprising asurfactant, a bleaching agent and magnesium sulfate, wherein thebleaching agent comprises a particulate peroxocarboxylic acid.
 12. Thecomposition according to claim 11, wherein the particulateperoxocarboxylic acid is present in an amount of 1% to 25% by weight,based on the composition.
 13. The composition according to claim 11,wherein the particulate peroxocarboxylic acid is present in an amount of2% to 20% by weight, based on the composition.
 14. The compositionaccording to claim 11, wherein the particulate peroxocarboxylic acid issolid at room temperature.
 15. The composition according to claim 11,wherein the particulate peroxocarboxylic acid is coated.
 16. Thecomposition according to claim 14, wherein the particulateperoxocarboxylic acid is coated.
 17. The composition according to claim12, wherein the particulate peroxocarboxylic acid is solid at roomtemperature.
 18. The composition according to claim 12, wherein theparticulate peroxocarboxylic acid is coated.
 19. The compositionaccording to claim 17, wherein the particulate peroxocarboxylic acid iscoated.
 20. The composition according to claim 11, wherein theparticulate peroxocarboxylic acid comprises a phthalimidoperoxyalkanoicacid.
 21. The composition according to claim 11, wherein the particulateperoxocarboxylic acid comprises 6-phthalimidoperoxyhexanoic acid. 22.The composition according to claim 12, wherein the particulateperoxocarboxylic acid comprises a phthalimidoperoxyalkanoic acid. 23.The composition according to claim 12, wherein the particulateperoxocarboxylic acid comprises 6-phthalimidoperoxyhexanoic acid. 24.The composition according to claim 11, wherein the magnesium sulfate ispresent in an amount of up to 30% by weight, based on the composition.25. The composition according to claim 12, wherein the magnesium sulfateis present in an amount of up to 30% by weight, based on thecomposition.
 26. The composition according to claim 11, wherein themagnesium sulfate is present in an amount of greater than 4% up to 20%by weight, based on the composition.
 27. The composition according toclaim 11, wherein the surfactant is present in an amount of 0.1% byweight to 50% by weight, based on the composition.
 28. The compositionaccording to claim 11, wherein the surfactant comprises a mixture of ananionic surfactant and a nonionic surfactant.
 29. The compositionaccording to claim 11, wherein the composition has a pH value of 2 to 6.30. The composition according to claim 11, wherein the particulateperoxocarboxylic acid and a liquid phase of the composition havedensities which differ from each other by no more than 10%.